Method of quenching electronic excitation of chromophore-containing organic molecules in photoactive compositions

ABSTRACT

The photostabilizing electronic excited state energy—particularly singlet state energy from a UV-absorbing molecule has been found to be readily transferred to (accepted by) α-cyanodiphenylacrylate compounds of formulas (I) and (V) having an alkoxy radical preferably in the four (para) position (hereinafter methoxycrylenes) on one or both of the phenyl rings: 
     
       
         
         
             
             
         
       
     
     wherein at least one of R 1  and R 2  is a straight or branched chain C 1 -C 12  alkoxy radical, preferably C 1 -C 8 , more preferably C 1 -C 4 , and most preferably methoxy, and any non-alkoxy radical R 1  or R 2  is hydrogen; and R 3  is a straight or branched chain C 1 -C 24  alkyl radical, preferably C 12 -C 24 , more preferably C 20 ; 
     
       
         
         
             
             
         
       
     
     wherein A and B are the same or different and are selected from the group consisting of oxygen, amino and sulfur; R 1  and R 3  are the same or different and are selected from the group consisting of C 1 -C 30  alkyl, C 2 -C 30  alkylene, C 2 -C 30  alkyne, C 3 -C 8  cycloalkyl, C 1 -C 30  substituted alkylene, C 2 -C 30  substituted alkyne, aryl, substituted aryl, heteroaryl, heterocycloalkyl, substituted heteroaryl and substituted heterocycloalkyl; R 2  is selected from the group consisting of C 1 -C 30  alkyl, C 2 -C 30  alkylene, C 2 C 30  alkyne, C 3 -C 8  cycloalkyl, C 1 -C 30  substituted alkyl, C 3 -C 8  substituted cycloalkyl, C 1 -C 30  substituted alkylene, C 2 -C 30  substituted alkyne; R 4 , R 5 , R 6  and R 7  are the same or different and are selected from the group consisting of C 1 -C 30  alkoxy straight chin on branched and a, b, c and d are each either 0 or 1, and a, b, c and d add up to 1, 2, 3, or 4.

FIELD OF THE INVENTION

The present invention is directed to a method of quenching electronicexcited state(s) of chromophore-containing UV-absorbing organicmolecules in photoactive compositions. More particularly, it has beenfound that α-cyano-β,β diphenylacrylates (crylenes) having an alkoxyradical, preferably on one of the phenyl rings (alternatively on bothphenyl rings), quenches the excited state of the chromophore byaccepting the excited state energy (singlet and sometimes also thetriplet state), thereby returning the UV-absorbing molecule back to itsground state so that the chromophore can absorb more photons, e.g., fromultraviolet (UV) light, thereby photostabilizing UV-absorbingchromophore-containing organic molecules, particularly butylmethoxydibenzoylmethane (Avobenzone), octyl methoxycinnamate(Octinoxate), and octyl salicylate (Octisalate) in photoactivecompositions.

BACKGROUND

The absorption of ultraviolet light by a chromophore-containing organicmolecule causes the excitation of an electron in the chromophore moietyfrom an initially occupied, low energy orbital to a higher energy,previously unoccupied orbital. The energy of the absorbed photon is usedto energize an electron and cause it to “jump” to a higher energyorbital, see Turro, Modern Molecular Photochemistry, 1991. Two excitedelectronic states derive from the electronic orbital configurationproduced by UV light absorption. In one state, the electron spins arepaired (antiparallel) and in the other state the electron spins areunpaired (parallel). The state with paired spins has no resultant spinmagnetic moment, but the state with unpaired spins possesses a net spinmagnetic moment. A state with paired spins remains a single state in thepresence of a magnetic field, and is termed a singlet state. A statewith unpaired spins interacts with a magnetic field and splits intothree quantized states, and is termed a triplet state.

In the electronically excited state, the chromophore-containing organicmolecule is prone to degrade via a number of known pathways and,therefore, can absorb little or no additional UV light. Tophotostabilize an electronically excited chromophore-containing organicmolecule in order to provide sufficient UV protection, it must bereturned to the ground state before it undergoes a photochemicalreaction destructive to its UV absorbing capability. There are knownphotostabilizing sunscreen additives, such as Octocrylene,methylbenzilydene camphor, and the esters or polyesters of naphthalenedicarboxylic acid of this assignee's U.S. Pat. Nos. 6,113,931;6,284,916; 6,518,451; and 6,551,605, all hereby incorporated byreference, that are capable of quenching excited triplet state energy.Surprisingly, it has been found that alkoxy crylenes, particularlymethoxy crylenes, return chromophore-containing organic molecules,particularly butyl methoxydibenzoylmethane (Avobenzone), octylmethoxycinnamate (Octinoxate), and octyl salicylate (Octisalate), fromboth an electronically excited singlet state and excited triplet stateback to their ground state, thereby photostabilizing the UV-absorbingorganic molecules.

Deflandre U.S. Pat. No. 5,576,354 generally discloses a cosmeticsunscreen composition containing at least 1% by weight of anα-cyano-β,β-diphenylacrylate that will photostabilize a dibenzoylmethanederivative, e.g., Parsol 1789 (Avobenzone), so long as the compositioncontains a fatty phase, e.g., glycerol stearates, isopropyl myristate orthe like, and so long as the mole ratio of theα-cyano-β,β-diphenylacrylate to the dibenzoylmethane derivative is atleast 0.8. The compounds preferred in the '354 patent and disclosed inthe examples are octocrylene, which contains no alkoxy radical(s)(UVINULN 539); β,β-bis(4-methoxyphenyl)acrylates (containing no cyanoradical); and the α-cyano-β,β-diphenylacrylates, which contain no alkoxyradical(s).

As stated in this assignees pending application Ser. Nos. 10/241,388;10/361,223; and 10/7865,793, an α-cyano-β,β-diphenylacrylate compound(e.g., octocrylene) is known to quench (accept) the excited tripletstate energy of an excited photoactive compound by dissipating theenergy kinetically in the form of rapid isomerizations. This process isshown below:

wherein the α-cyano-β,β-diphenylacrylate compound (octocrylene shownabove as structure A), accepts the triplet excited state energy from aphotoactive compound and forms a diradical (shown above as structure A*)at the α and β positions of the acrylate, which converts the double bondinto a single bond and allows for the free rotation of the phenylgroups. This rotation occurs rapidly and efficiently to dissipate anyexcited triplet state energy accepted by theα-cyano-β,β-diphenylacrylate compound from the photoactive compound.

While octocrylene is able to quench (accept) the triplet excited stateenergy from a photoactive compound, thereby photostabilizing, to somedegree, dibenzoylmethane derivatives, as shown in examples 1, 4, 6 and 8of Deflandre et al. U.S. Pat. No. 5,576,354, hereby incorporated byreference, there exists a need in the photoactive composition art tofind one or more compounds that quench (accept) the singlet excitedstate energy and preferably also the triplet excited state energy fromphotoactive compounds, which octocrylene does not.

Quite surprisingly, it has been found that the alkoxy substitutedα-cyano-β,β-diphenylacrylates (alkoxy crylenes) will quench theelectronically excited singlet state energy of UV-absorbing organicmolecules, such as the dibenzoylmethane derivatives of U.S. Pat. No.5,576,354, even at very low loadings compared to the quantity ofUV-absorbing compounds.

SUMMARY

The photostabilizing electronic excited state energy—particularlysinglet state energy from a UV-absorbing molecule—has been found to bereadily transferred to (accepted by) α-cyanodiphenylacrylate compoundshaving an alkoxy radical in the four (para) position (hereinafter“alkoxycrylenes”) on one or both of the phenyl rings having the formula(I):

wherein one or both of R₁ and R₂ is a straight or branched chain C₁-C₃₀alkoxy radical, preferably C₁-C₈, more preferably methoxy, and anynon-alkoxy radical R₁ or R₂ is hydrogen; and R₃ is a straight orbranched chain C₁-C₃₀ alkyl radical, preferably C₂-C₂₀.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph showing the photostability of the sunscreencompositions of Examples 1-3 (when irradiated with 35 MED of UVradiation) provided by 4.5% octyldocedyl methoxy crylene (C2OMC); and2.75% Octocrylene (OC) compared to the photostability prior to UVirradiation and compared to the composition with no photostabilizer;

FIG. 2 is a graph showing the photostability of the sunscreencomposition of Example 4 before and after irradiation with 35 MED of UVradiation;

FIG. 3 is a graph showing the photostability of the sunscreencomposition of Example 5 before and after irradiation with 35 MED of UVradiation; and

FIG. 4 is a graph showing the photostability of the sunscreencomposition of Example 6 before and after irradiation with 35 MED of UVradiation; and

FIG. 5 is a graph showing the sunscreen composition of Example 7 beforeand after irradiation with 35 MED of UV radiation.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Ranges may be expressed herein as from “about” or “approximately” oneparticular value and/or to “about” or “approximately” another particularvalue. When such a range is expressed, another embodiment includes fromthe one particular value and/or to the other particular value.Similarly, when values are expressed as approximations, by use of theantecedent “about,” it will be understood that the particular valueforms another embodiment. The term “alkoxy” herein refers to a radicalextending from the para position of one or both of the phenyl ringshaving the formula O—R, wherein R is an alkyl radical, straight chain orbranched having 1 to 30 carbon atoms, preferably wherein R═C₁ to C₈,more preferably C₂-C₂₀, and most preferably —O—CH₃ (methoxy). The oxygenatom of the alkoxy radical is covalently bonded to the para carbon atomof one or both of the phenyl rings, preferably only one of the phenyls,preferably having the formula (II) or (III):

wherein R₃ is as previously defined.

The term “crylene” as used herein refers to a chromophoric moiety thatincludes an α-cyano-β,β-diphenyl propanoic acid ester.

The term “cyano” as used herein refers to a —C—N group, also designated“—CN.”

Photoactive compositions, e.g., sunscreen compositions, generallyinclude UV-A and UV-B photoactive compounds in a cosmetically acceptablecarrier, optionally including additives, such as emollients,stabilizers, emulsifiers, and combinations thereof. These additives canbe used in preparing a UV filter composition in an emulsion(oil-in-water or water-in-oil) from a composition that includes one ormore photoactive compounds and a solvent or a solvent combination thatincludes one or more organic solvents and water. When made, preferablythe emulsion is an oil-in-water emulsion, wherein the oil phase isprimarily formed from a mixture of the UV filter compound(s) and one ormore organic solvents.

A typical photoactive composition includes one or more photoactivecompounds, wherein the photoactive compound(s) act to absorb UVradiation and thereby protect the substrate (e.g., human skin, resins,films, and the like) from the harmful effects of UV radiation. Theabsorption process causes a photoactive compound to reach an excitedstate, wherein the excited state is characterized by the presence ofexcited electronic energy (e.g., singlet state energy or triplet stateenergy), as compared to the ground state of the photoactive compound.Once a photoactive compound reaches an excited state there exists anumber of pathways by which the excited photoactive compound candissipate its excess energy (e.g., singlet and/or triplet energy),however, many of those pathways adversely affect the ability of thephotoactive compound to further absorb UV radiation. The alkoxy crylenemolecules described herein accept electronic singlet excited stateenergy from UV-absorbers, particularly Avobenzone, octylmethoxycinnamate (Octinoxate), and octyl salicylate (Octisalate). Thealkoxy crylenes also are very effective UV absorbers in addition toproviding electronic singlet state energy quenching of otherUV-absorbing compounds in sunscreen compositions. The alkoxy crylenemolecules described herein are especially effective when combined withone or more additional electronic singlet excited state quenchingcompounds such as oxybenzone. Particularly surprising photostabilizationis achieved in sunscreen compositions containing the alkoxy crylenemolecules described herein together with octyl methoxycinnamate andAvobenzone.

A photoactive compound is one that responds to light photoelectrically.In the compositions and methods of photostabilization disclosed herein,a photoactive compound is one that responds to UV radiationphotoelectrically. For example, all photoactive compound-containingcompositions that respond to UV radiation photoelectrically byphotoactive compound photodegradation benefit highly by the inclusion ofthe alkoxy crylene molecules described herein. The alkoxy crylenesdescribed herein are useful photostabilizers and/or photoactivecompounds when combined with any single or combination photoactivecompounds identified in Shaath, Nadim, Encyclopedia of UV filters,©2007, hereby incorporated by reference. Photostability is a problemwith all UV filters because they all reach an electronic singlet excitedstate upon exposure to UV radiation.

It is theorized that the following UV filters are photostabilized by thealkoxy crylene molecules described herein, including all of thefollowing, including combinations of any two or more, and includecompounds selected from the following categories (with specificexamples) including: p-aminobenzoic acid, its salts and its derivatives(ethyl, isobutyl, glyceryl esters; p-dimethylaminobenzoic acid);anthranilates (o-aminobenzoates; methyl, menthyl, phenyl, benzyl,phenylethyl, linalyl, terpinyl, and cyclohexenyl esters); salicylates(octyl, amyl, phenyl, benzyl, menthyl (homosalate), glyceryl, anddipropyleneglycol esters); cinnamic acid derivatives (menthyl and benzylesters, alpha-phenyl cinnamonitrile; butyl cinnamoyl pyruvate);dihydroxycinnamic acid derivatives (umbelliferone, methylumbelliferone,methylaceto-umbelliferone); camphor derivatives (3 benzylidene, 4methylbenzylidene, polyacrylamidomethyl benzylidene, benzalkoniummethosulfate, benzylidene camphor sulfonic acid, and terephthalylidenedicamphor sulfonic acid); trihydroxycinnamic acid derivatives(esculetin, methylesculetin, daphnetin, and the glucosides, esculin anddaphnin); hydrocarbons (diphenylbutadiene, stilbene); dibenzalacetone;benzalacetophenone; naphtholsulfonates (sodium salts of2-naphthol-3,6-disulfonic and of 2-naphthol-6,8-disulfonic acids);dihydroxy-naphthoic acid and its salts; o- andp-hydroxydiphenyldisulfonates; coumarin derivatives (7-hydroxy,7-methyl, 3-phenyl); diazoles (2-acetyl-3-bromoindazole, phenylbenzoxazole, methyl naphthoxazole, various aryl benzothiazoles); quininesalts (bisulfate, sulfate, chloride, oleate, and tannate); quinolinederivatives (8-hydroxyquinoline salts, 2-phenylquinoline); hydroxy- ormethoxy-substituted benzophenones; uric acid derivatives; vilouric acidderivatives; tannic acid and its derivatives; hydroquinone; andbenzophenones (oxybenzone, sulisobenzone, dioxybenzone, benzoresorcinol,octabenzone, 4-isopropyldibenzoyl methane, butylmethoxydibenzoylmethane,etocrylene, and 4-isopropyl-dibenzoylmethane).

The following UV filters should be particularly photostabilized by thealkoxy crylene molecules described herein: 2-ethylhexylp-methoxycinnamate, 4,4′-t-butyl methoxydibenzoylmethane, octyldimethylp-aminobenzoate, digalloyltrioleate, ethyl4-[bis(hydroxypropyl)]aminobenzoate, 2-ethylhexylsalicylate, glycerolp-aminobenzoate, 3,3,5-trimethylcyclohexylsalicylate, and combinationsthereof.

Photoactive compositions disclosed herein can include a variety ofphotoactive compounds, preferably including one or more UV-A photoactivecompounds and one or more UV-B photoactive compounds. Preferably, asunscreen composition includes a photoactive compound selected from thegroup consisting of p-aminobenzoic acid and salts and derivativesthereof; anthranilate and derivatives thereof; dibenzoylmethane andderivatives thereof; salicylate and derivatives thereof; cinnamic acidand derivatives thereof; dihydroxycinnamic acid and derivatives thereof;camphor and salts and derivatives thereof; trihydroxycinnamic acid andderivatives thereof; dibenzalacetone naphtholsulfonate and salts andderivatives thereof; benzalacetophenone naphtholsulfonate and salts andderivatives thereof; dihydroxy-naphthoic acid and salts thereof;o-hydroxydiphenyldisulfonate and salts and derivatives thereof;p-hydroxydiphenyldisulfonate and salts and derivatives thereof; coumarinand derivatives thereof; diazole derivatives; quinine derivatives andsalts thereof; quinoline derivatives; uric acid derivatives; vilouricacid derivatives; tannic acid and derivatives thereof; hydroquinone;diethylamino hydroxybenzoyl hexyl benzoate and salts and derivativesthereof; and combinations of the foregoing.

UV A radiation (about 320 nm to about 400 nm), is recognized ascontributing to causing damage to skin, particularly to very lightlycolored or sensitive skin. A sunscreen composition disclosed hereinpreferably includes a UV-A photoactive compound. Preferably, a sunscreencomposition disclosed herein includes a dibenzoylmethane derivative UV-Aphotoactive compound. Preferred dibenzoylmethane derivatives include,2-methyldibenzoylmethane; 4-methyldibenzoylmethane;4-isopropyldibenzoylmethane; 4-tert-butyldibenzoylmethane;2,4-dimethyldibenzoylmethane; 2,5-dimethyldibenzoylmethane;4,4′-diisopropyldibenzoylmethane; 4,4′-dimethoxydibenzoylmethane;4-tert-butyl-4′-methoxydibenzoylmethane;2-methyl-5-isopropyl-4′-methoxydibenzoylmethane;2-methyl-5-tert-butyl-4′-methoxydibenzoylmethane;2,4-dimethyl-4′-methoxydibenzoylmethane;2,6-dimethyl-4-tert-butyl-4′-methoxydibenzoyl methane, and combinationsthereof.

For a product marketed in the United States, preferred cosmeticallyacceptable photoactive compounds and concentrations (reported as apercentage by weight of the total cosmetic sunscreen composition)include: aminobenzoic acid (also called para aminobenzoic acid and PABA;15% or less), Avobenzone (also called butyl methoxy dibenzoylmethane; 3%or less), cinoxate (also called 2 ethoxyethyl p methoxycinnamate; 3% orless), dioxybenzone (also called benzophenone 8; 3% or less), homosalate((also called 3,3,5-trimethylcyclohexyl salicylate, 15% or less),menthyl anthranilate (also called menthyl 2 aminobenzoate; 5% or less),octocrylene (also called 2 ethylhexyl 2 cyano 3,3 diphenylacrylate; 10%or less), octyl methoxycinnamate (7.5% or less), octyl salicylate (alsocalled 2 ethylhexyl salicylate; 5% or less), oxybenzone (also calledbenzophenone 3; 6% or less), padimate O (also called octyl dimethylPABA; 8% or less), phenylbenzimidazole sulfonic acid (water soluble; 4%or less), sulisobenzone (also called benzophenone 4; 10% or less),titanium dioxide (25% or less), trolamine salicylate (also calledtriethanolamine salicylate; 12% or less), and zinc oxide (25% or less).

Other preferred cosmetically acceptable photoactive compounds andpreferred concentrations (percent by weight of the total cosmeticsunscreen composition) include diethanolamine methoxycinnamate (10% orless), ethyl-[bis(hydroxypropyl)] aminobenzoate (5% or less), glycerylaminobenzoate (3% or less), 4 isopropyl dibenzoylmethane (5% or less), 4methylbenzylidene camphor (6% or less), terephthalylidene dicamphorsulfonic acid (10% or less), and sulisobenzone (also called benzophenone4, 10% or less).

For a product marketed in the European Union, preferred cosmeticallyacceptable photoactive compounds and preferred concentrations (reportedas a percentage by weight of the total cosmetic sunscreen composition)include: PABA (5% or less), camphor benzalkonium methosulfate (6% orless), homosalate (10% or less), benzophenone 3 (10% or less),phenylbenzimidazole sulfonic acid (8% or less, expressed as acid),terephthalidene dicamphor sulfonic acid (10% or less, expressed asacid), butyl methoxydibenzoylmethane (5% or less), benzylidene camphorsulfonic acid (6% or less, expressed as acid), octocrylene (10% or less,expressed as acid), polyacrylamidomethyl benzylidene camphor (6% orless), ethylhexyl methoxycinnamate (10% or less), PEG 25 PABA (10% orless), isoamyl p methoxycinnamate (10% or less), ethylhexyl triazone (5%or less), drometrizole trielloxane (15% or less), diethylhexyl butamidotriazone (10% or less), 4 methylbenzylidene camphor (4% or less), 3benzylidene camphor (2% or less), ethylhexyl salicylate (5% or less),ethylhexyl dimethyl PABA (8% or less), benzophenone 4 (5%, expressed asacid), methylene bis benztriazolyl tetramethylbutylphenol (10% or less),disodium phenyl dibenzimidazole tetrasulfonate (10% or less, expressedas acid), bis ethylhexyloxyphenol methoxyphenol triazine (10% or less),methylene bisbenzotriazolyl tetramethylbutylphenol (10% or less, alsocalled TINOSORB M or Bisoctrizole), and bisethylhexyloxyphenolmethoxyphenyl triazine. (10% or less, also called TINOSORB S orBemotrizinol).

All of the above described UV filters are commercially available. Forexample, suitable commercially available organic UV filters areidentified by trade name and supplier in Table I below:

TABLE I CTFA Name Trade Name Supplier benzophenone-3 UVINUL M-40 BASFChemical Co. benzophenone-4 UVINUL MS-40 BASF Chemical Co.benzophenone-8 SPECTRA-SORB UV-24 American Cyanamid DEA-methoxycinnamateBERNEL HYDRO Bernel Chemical diethylamino hydroxybenzoyl hexyl UVINULA-PLUS BASF Chemical Co. benzoate diethylhexyl butamido triazone UVISORBHEB 3V-Sigma disodium phenyl dibenzylimidazole NEO HELIOPAN AP Symriseethyl dihydroxypropyl-PABA AMERSCREEN P Amerchol Corp. glyceryl PABANIPA G.M.P.A. Nipa Labs. homosalate KEMESTER HMS Humko Chemical menthylanthranilate SUNAROME UVA Felton Worldwide octocrylene UVINUL N-539 BASFChemical Co. octyl dimethyl PABA AMERSCOL Amerchol Corp. octylmethoxycinnamate PARSOL MCX Bernel Chemical PABA PABA National Starch2-phenylbenzimidazole-5- EUSOLEX 6300 EM Industries sulphonic acid TEAsalicylate SUNAROME W Felton Worldwide 2-(4-methylbenzildene)-camphorEUSOLEX 6300 EM Industries benzophenone-1 UVINUL 400 BASF Chemical Co.benzophenone-2 UVINUL D-50 BASF Chemical Co. benzophenone-6 UVINUL D-49BASF Chemical Co. benzophenone-12 UVINUL 408 BASF Chemical Co.4-isopropyl dibenzoyl methane EUSOLEX 8020 EM Industries butyl methoxydibenzoyl methane PARSOL 1789 Givaudan Corp. etocrylene UVINUL N-35 BASFChemical Co. methylene bisbenzotriazolyl TINOSORB M Ciba Specialtytetramethylbutylphenol Chemicals bisethylhexyloxyphenol TINOSORB S CibaSpecialty methoxyphenyl triazine. Chemicals

Commonly-assigned U.S. Pat. Nos. 6,485,713 and 6,537,529, thedisclosures of which are hereby incorporated herein by reference,describe compositions and methods for increasing the photostability ofphotoactive compounds in a sunscreen composition, e.g., by the additionof polar solvents to the oil phase of a composition. By increasing thepolarity of the oil phase of a sunscreen composition including thealkoxy crylenes described herein, e.g., methoxy crylene, the stabilityof the sunscreen composition is surprisingly increased in comparison tooctocrylene. In the sunscreen compositions described herein, preferably,one or more of a highly polar solvent is present in the oil-phase of thecomposition. Preferably, a sufficient amount of a polar solvent ispresent in the sunscreen composition to raise the dielectric constant ofthe oil-phase of the composition to a dielectric constant of at leastabout 7, preferably at least about 8. With or without the highly polarsolvent in the oil phase, the methoxy crylene molecules described hereinyield unexpected photostability in comparison to octocrylene.

A photoactive compound can be considered stable when, for example, after30 MED irradiation the photoactive compound has retained at least about90% of its original absorbance at a wavelength, or over a range ofwavelengths of interest (e.g., the wavelength at which a photoactivecompound has a peak absorbance, such as 350-370 nm for Avobenzone).Likewise, a sunscreen composition can include a plurality of photoactivecompounds and a sunscreen composition, as a whole, can be consideredstable when, for example, after 30 MED irradiation the sunscreencomposition has retained at least about 90% of its original absorbanceat one or more wavelengths of interest (e.g., at or near the peakabsorbance wavelength of the primary photoactive compound).

In accordance with one important embodiment, an alkoxycrylene of formula(I) is combined in a sunscreen or dermatological formulation with awater soluble UV filter compound and/or a broad-band filter compound andoptionally, but preferably, together with a dibenzoylmethane derivativeand/or a dialkyl naphthalate.

Advantageous water-soluble UV filter substances for the purposes of thepresent invention are sulfonated UV filters, in particular:phenylene-1,4-bis(2-benzimidazyl)-3,3′-5,5′-tetrasulfonic acid, whichhas the following structure:

and its salts, especially the corresponding sodium, potassium ortriethanolammonium salts, in particularphenylene-1,4-bis(2-benzimidazyl)-1-3,3′-5,5′-tetrasulfonic acidbissodium salt

with the INCI name disodium phenyl dibenzimidazole tetrasulfonate (CASNo.: 180898-37-7), which is obtainable for example under the proprietaryname Neo Heliopan A P from Haarmann & Reimer.

Further advantageous sulfonated UV filters for the purposes of thepresent invention are the salts of 2-phenylbenzimidazole-5-sulfonicacid, such as its sodium, potassium or its triethanolammonium salts, andthe sulfonic acid itself

with the INCI name phenylbenzimidazole sulfonic acid (CAS No.27503-81-7), which is obtainable for example under the proprietary nameEusolex 232 from Merck or under Neo Heliopan Hydro from Haarmann &Reimer.

Further advantageous water-soluble UV-B and/or broad-band filtersubstances for the purposes of the present invention are, for example,sulfonic acid derivatives of 3-benzylidenecamphor, such as, for example,4-(2-oxo-3-bornylidenemethyl)benzene-sulfonic acid,2-methyl-5-(2-oxo-3-bornylidenemethyl)sulfonic acid and the saltsthereof.

The total amount of one or more water-soluble UV filter substances inthe finished cosmetic or dermatological preparations is advantageouslychosen from the range 0.01% by weight to 20% by weight, preferably from0.1 to 10% by weight, in each case based on the total weight of thepreparations.

In accordance with another important embodiment, an alkoxycrylene offormula (I) is combined in a sunscreen or dermatological formulationwith a hydroxybenzophenone compound and/or a broad-band filter compoundand optionally, but preferably, together with a dibenzoylmethanederivative and/or a dialkyl naphthalate.

With an alkoxycrylene, it is possible to completely dispense with theuse of other UV stabilizers, in particular the use ofethylhexyl-2-cyano-3,3-diphenylacrylate(octocrylene) or4-methylbenzylidenecamphor.

Hydroxybenzophenones are characterized by the following structuralformula:

where R¹ and R² independent of one another are hydrogen, C₁-C₂₀-alkyl,C₃-C₁₀-cycloalkyl or C₃-C₁₀-cyloalkenyl, wherein the substituents R¹ andR² together with the nitrogen atom to which they are bound can form a 5-or 6-ring and R³ is a C₁-C₂0 alkyl radical.

A particularly advantageous hydroxybenzophenone is the2-(4′-diethylamino-2′-hydroxybenzoyl)benzoic acid hexyl ester (also:aminobenzophenone) which is characterized by the following structure:

and is available from BASF under the Uvinul A Plus.

According to the invention, cosmetic or dermatological preparationscontain 0.1 to 20% by weight, advantageously 0.1 to 15% by weight, veryparticularly preferred 0.1 to 10% by weight, of one or morehydroxybenzophenones.

Within the scope of the present invention, dialkyl naphthalates forwhich R¹ and/or R² represent branched alkyl groups with 6 to 10 carbonatoms are advantageous. Within the scope of the present inventiondiethylhexyl naphthalate is very particularly preferred which isavailable, e.g., under the trade name Hallbrite TQ™ from CP Hall orCorapan TQ™ from H&R.

According to one embodiment of the invention cosmetic or dermatologicalpreparations advantageously contain 0.001 to 30% by weight, preferably0.01 to 20% by weight, very particularly preferred 0.5 to 15% by weight,of one or more dialkyl naphthalates.

The cosmetic or dermatological light-protection formulations accordingto the invention can be composed as usual and be used for cosmetic ordermatological light-protection, furthermore for the treatment, care andcleansing of the skin and/or hair and as a cosmetic product indecorative cosmetics.

In accordance with another important embodiment, an alkoxycrylene offormula (I) is combined in a sunscreen or dermatological formulationwith a benzotriazole derivatives compound and/or a broad-band filtercompound and optionally, but preferably, together with adibenzoylmethane derivative and/or a dialkyl naphthalate.

An advantageous benzotriazole derivative is2,2′-methylenebis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol),which has the chemical structural formula

(INCI: bisoctyltriazole). It is obtainable under the proprietary nameTinosorb® from CIBA-Chemikalien GmbH and is distinguished by good UVabsorption properties. The disadvantage of this substance is thecharacteristic of forming imperceptibly thin films on the skin whichhave unpleasant tactile properties.

Another disadvantage is that such benzotriazole derivatives show onlyinadequate solubility, if any, in conventional oil components.Well-known solvents can dissolve only up to a maximum of 15% by weightof these compounds, which usually corresponds to a concentration ofabout 1 to 1.5% by weight of dissolved (=active) filter substance in thecomplete cosmetic or dermatological preparation.

One disadvantage of the prior art is accordingly that generally onlycomparatively low sun protection factors have been achievable with thesefilter substances because their solubility or dispersibility in theformulations is too low, i.e. they can be satisfactorily incorporatedinto such formulations only with difficulty or not at all.

Even if it is also possible in principle to achieve a certain UVprotection when the solubility is limited, another problem frequentlyoccurs, that is recrystallization.

Substances of low solubility in particular recrystallize comparativelyrapidly, which may be induced by fluctuations in temperature or otherinfluences. Uncontrolled recrystallization of an essential ingredient ofa preparation such as a UV filter has, however, extremelydisadvantageous effects on the properties of the given preparation and,not least, on the desired light protection.

In accordance with another embodiment, the alkoxycrylene-containingcompositions described herein can contain an increased content ofunsymmetrically substituted triazine derivatives when combined togetherwith an alkoxycrylene of formula (I) to obtain an increased sunprotection factor.

It was, however, surprising and not predictable for the skilled workerthat the disadvantages of the prior art are remedied by activeingredient combinations effective for light protection and composed of

(a) one or more UV filter substances selected from the group ofbenzotriazole derivatives;(b) an alkoxycrylene of formula (I); and optionally(c) one or more dialkyl naphthalates having the structural formula:

in which R¹ and R² are, independently of one another, selected from thegroup of branched and unbranched alkyl groups having 6 to 24 carbonatoms.

Particularly advantageous light protection filters for the purpose ofthis embodiment of the present invention include a benzotriazolecompound having a structural formula:

where R₁ and R₂ are, independently of one another, selected from thegroup of branched or unbranched C₁-C₁₈-alkyl radicals, ofC₅-C₁₂-cycloalkyl or aryl radicals which are optionally substituted byone or more C₁-C₄ alkyl groups.

The preferred benzotriazole derivative is2,2′-methylenebis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol)which is characterized by the chemical structural formula:

An advantageous broadband filter for the purpose of the presentinvention is moreover2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3-tetramethyl-1-[(trimethyl-silyl)oxy]disiloxanyl]propyl]phenol(CAS No.: 155633-54-8) with the INCI name drometrizole trisiloxane,which is characterized by the chemical structural formula

The total amount of one or more benzotriazole derivatives, in particularof2,2′-methylenebis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol)and/or2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propyl]phenol,in the finished cosmetic or dermatological preparations isadvantageously chosen from the range from 0.1 to 15.0% by weight,preferably 0.5 to 10.0% by weight, based on the total weight of thepreparations.

The cosmetic or dermatological light protection formulations of theinvention may have conventional compositions and be used for cosmetic ordermatological light protection and for the treatment, care andcleansing of skin and/or the hair and as a make-up product in decorativecosmetics.

For use, the cosmetic and dermatological preparations are applied to theskin and/or the hair in a sufficient quantity in the manner customaryfor cosmetics.

Cosmetic and dermatological preparations according to the invention cancomprise cosmetic auxiliaries such as those conventionally used in suchpreparations, e.g. preservatives, bactericides, perfumes, antifoams,dyes, pigments which have a coloring effect, thickeners, moisturizersand/or humectants, fats, oils, waxes or other conventional constituentsof a cosmetic or dermatological formulation, such as alcohols, polyols,polymers, foam stabilizers, electrolytes, organic solvents or siliconederivatives.

An additional content of antioxidants is generally preferred. Accordingto the invention, favorable antioxidants which can be used are anyantioxidants suitable or conventional for cosmetic and/or dermatologicalapplications.

The antioxidants are particularly advantageously chosen from the groupconsisting of amino acids (e.g. glycine, histidine, tyrosine,tryptophan) and derivatives thereof, imidazoles (e.g. urocanic acid) andderivatives thereof, peptides such as D,L-carnosine, D-carnosine,L-carnosine and derivatives thereof (e.g. anserine), carotenoids,carotenes (e.g. .alpha.-carotene, .beta.-carotene, lycopene) andderivatives thereof, chlorogenic acid and derivatives thereof, lipoicacid and derivatives thereof (e.g. dihydrolipoic acid), aurothioglucose,propylthiouracil and other thiols (e.g. thioredoxin, glutathione,cysteine, cystine, cystamine and the glycosyl, N-acetyl, methyl, ethyl,propyl, amyl, butyl and lauryl, palmitoyl, oleyl, .gamma.-linoleyl,cholesteryl and glyceryl esters thereof) and salts thereof, dilaurylthiodipropionate, distearyl thiodipropionate, thiodipropionic acid andderivatives thereof (esters, ethers, peptides, lipids, nucleotides,nucleosides and salts) and sulfoximine compounds (e.g. buthioninesulfoximines, homocysteine sulfoximine, buthionine sulfones, penta-,hexa-, heptathionine sulfoximine) in very low tolerated doses (e.g. pmolto .mu.mol/kg), and also (metal) chelating agents (e.g. alpha.-hydroxyfatty acids, palmitic acid, phytic acid, lactoferrin), .alpha.-hydroxyacids (e.g. citric acid, lactic acid, malic acid), humic acid, bileacid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and derivativesthereof, unsaturated fatty acids and derivatives thereof (e.g.gamma.-linolenic acid, linoleic acid, oleic acid), folic acid andderivatives thereof, ubiquinone and ubiquinol and derivatives thereof,vitamin C and derivatives (e.g. ascorbyl palmitate, Mg ascorbylphosphate, ascorbyl acetate), tocopherols and derivatives (e.g. vitaminE acetate), vitamin A and derivatives (vitamin A palmitate) andconiferyl benzoate of gum benzoin, rutinic acid and derivatives thereof,.alpha.-glycosylrutin, ferulic acid, furfurylideneglucitol, carnosine,butylhydroxytoluene, butylhydroxyanisole, nordihydroguaiaretic acid,trihydroxybutyro-phenone, uric acid and derivatives thereof, mannose andderivatives thereof, zinc and derivatives thereof (e.g. ZnO, ZnSO₄),selenium and derivatives thereof (e.g. selenomethionine), stilbenes andderivatives thereof (e.g. stilbene oxide, trans-stilbene oxide) and thederivatives (salts, esters, ethers, sugars, nucleotides, nucleosides,peptides and lipids) of said active ingredients which are suitableaccording to the invention.

In accordance with another important embodiment, an alkoxycrylene offormula (I) is combined in a sunscreen or dermatological formulationwith hydrophilic skincare active ingredients and/or a broad-band filtercompound and optionally, but preferably, together with adibenzoylmethane derivative.

Advantageous hydrophilic active ingredients which (individually or inany combinations with one another) are stabilized by their use togetherwith an alkoxycrylene according to the invention include those listedbelow:

biotin; carnitine and derivatives; creatine and derivatives; folic acid;pyridoxine niacinamide; polyphenols (in particular flavonoids, veryparticularly alpha-glucosylrutin) ascorbic acid and derivatives;Hamamelis; Aloe Vera; panthenol; amino acids.

Particularly advantageous hydrophilic active ingredients for thepurposes of the present invention are also water-soluble antioxidants,such as, for example, vitamins.

The amount of hydrophilic active ingredients (one or more compounds) inthe preparations is preferably 0.0001 to 10% by weight, particularlypreferably 0.001 to 5% by weight, based on the total weight of thepreparation.

Particularly advantageous preparations are also obtained whenantioxidants are used as additives or active ingredients. According tothe invention, the preparations advantageously comprise one or moreantioxidants. Favorable, but nevertheless optional antioxidants whichmay be used are all antioxidants customary or suitable for cosmeticand/or dermatological applications.

The amount of antioxidants (one or more compounds) in the preparationsis preferably 0.001 to 30% by weight, particularly preferably 0.05 to20% by weight, in particular 0.1 to 10% by weight, based on the totalweight of the preparation.

If vitamin E and/or derivatives thereof are the antioxidant orantioxidants, it is advantageous to choose their respectiveconcentrations from the range from 0.001 to 10% by weight, based on thetotal weight of the formulation.

If vitamin A or vitamin A derivatives, or carotenes or derivativesthereof are the antioxidant or antioxidants, it is advantageous tochoose their respective concentrations from the range from 0.001 to 10%by weight, based on the total weight of the formulation.

It is particularly advantageous when the cosmetic preparations accordingto the present invention comprise further cosmetic or dermatologicalactive ingredients, preferred active ingredients being antioxidantswhich can protect the skin against oxidative stress.

Advantageous further active ingredients are natural active ingredientsand/or derivatives thereof, such as e.g. ubiquinones, retinoids,carotenoids, creatine, taurine and/or .beta.-alanine.

Formulations according to the invention, which comprise e.g. knownantiwrinkle active ingredients, such as flavone glycosides (inparticular .alpha.-glycosylrutin), coenzyme Q10, vitamin E and/orderivatives and the like, are particularly advantageously suitable forthe prophylaxis and treatment of cosmetic or dermatological changes inskin, as arise, for example, during skin aging (such as, for example,dryness, roughness and formation of dryness wrinkles, itching, reducedrefatting (e.g. after washing), visible vascular dilations(teleangiectases, couperosis), flaccidity and formation of wrinkles andlines, local hyperpigmentation, hypopigmentation and abnormalpigmentation (e.g. age spots), increased susceptibility to mechanicalstress (e.g. cracking) and the like). In addition, they areadvantageously suitable against the appearance of dry or rough skin.

In accordance with still another important embodiment, an alkoxycryleneof formula (I) is combined in a sunscreen or dermatological formulationwith particulate UV filter substances and/or a broad-band filtercompound and optionally, but preferably, together with adibenzoylmethane derivative and/or a dialkyl naphthalate.

Preferred particulate UV filter substances for the purposes of thepresent invention are inorganic pigments, especially metal oxides and/orother metal compounds which are slightly soluble or insoluble in water,especially oxides of titanium (TiO₂), zinc (ZnO), iron (e.g. Fe₂O₃),zirconium (ZrO₂), silicon (SiO₂), manganese (e.g. MnO), aluminum(A)₂O₃), cerium (e.g. Ce₂O₃), mixed oxides of the corresponding metals,and mixtures of such oxides, and the sulfate of barium (BaSO₄).

Zinc oxides for the purposes of the present invention may also be usedin the form of commercially available oily or aqueous predispersions.Zinc oxide particles and predispersions of zinc oxide particles whichare suitable according to the invention are distinguished by a primaryparticle size of <300 nm and can be obtained under the followingproprietary names from the stated companies:

Proprietary name Coating Manufacturer Z-Cote HP1 2% Dimethicone BASFZ-Cote / BASF ZnO NDM 5% Dimethicone H&R ZnO Neutral / H&R MZ-300 /Tayca Corporation MZ-500 / Tayca Corporation MZ-700 / Tayca CorporationMZ-303S 3% Methicone Tayca Corporation MZ-505S 5% Methicone TaycaCorporation MZ-707S 7% Methicone Tayca Corporation MZ-303M 3%Dimethicone Tayca Corporation MZ-505M 5% Dimethicone Tayca CorporationMZ-707M 7% Dimethicone Tayca Corporation Z-Sperse Ultra ZnO (>=56%)/Ethylhexyl Collaborative Hydroxystearate Benzoate/ LaboratoriesDimethicone/Cyclomethicone Samt-UFZO- ZnO (60%)/ Miyoshi Kasei 450/D5(60%) Cyclomethicone/Dimethicone

Particularly preferred zinc oxides for the purposes of the invention areZ-Cote HPI and Z-Cote from BASF and zinc oxide NDM from Haarmann &Reimer.

Titanium dioxide pigments of the invention may be in the form of boththe rutile and anatase crystal modification and may for the purposes ofthe present invention advantageously be surface-treated (“coated”), theintention being for example to form or retain a hydrophilic, amphiphilicor hydrophobic character. This surface treatment may consist ofproviding the pigments by processes known per se with a thin hydrophilicand/or hydrophobic inorganic and/or organic layer. The various surfacecoatings may for the purposes of the present invention also containwater.

Inorganic surface coatings for the purposes of the present invention mayconsist of aluminum oxide (Al.sub.20.sub.3), aluminum hydroxideAl(OH).sub.3 or aluminum oxide hydrate (also: alumina, CAS No.:1333-84-2), sodium hexametaphosphate

(NaPO.sub.3).sub.6, sodium metaphosphate (NaPO.sub.3).sub.n, silicondioxide (SiO.sub.2) (also: silica, CAS No.: 7631-86-9), or iron oxide(Fe.sub.20.sub.3). These inorganic surface coatings may occur alone, incombination and/or in combination with organic coating materials.

Organic surface coatings for the purposes of the present invention mayconsist of vegetable or animal aluminum stearate, vegetable or animalstearic acid, lauric acid, dimethylpolysiloxane (also: dimethicones),methylpolysiloxane (methicones), simethicones (a mixture ofdimethylpolysiloxane with an average chain length of from 200 to 350dimethylsiloxane units and silica gel) or alginic acid. These organicsurface coatings may occur alone, in combination and/or in combinationwith inorganic coating materials.

Coated and uncoated titanium dioxides of the invention may be used inthe form of commercially available oily or aqueous predispersions. Itmay be advantageous to add dispersion aids and/or solubilizationmediators.

Suitable titanium dioxide particles and predispersions of titaniumdioxide particles for the purposes of the present invention areobtainable under the following proprietary names from the statedcompanies:

Additional ingredients of the Proprietary name Coating predispersionManufacturer MT-150W None — Tayca Corporation MT-150A None — TaycaCorporation MT-500B None — Tayca Corporation MT-600B None — TaycaCorporation MT-100TV Aluminum — Tayca Corporation hydroxide Stearic acidMT-100Z Aluminum — Tayca Corporation hydroxide Stearic acid MT-100TAluminum — Tayca Corporation hydroxide Stearic acid MT-500T Aluminum —Tayca Corporation hydroxide Stearic acid MT-100S Aluminum — TaycaCorporation hydroxide Lauric acid MT-100F Stearic acid Iron — TaycaCorporation oxide MT-100SA Alumina Silica — Tayca Corporation MT-500SAAlumina Silica — Tayca Corporation MT-600SA Alumina Silica — TaycaCorporation MT-100SAS Alumina Silica — Tayca Corporation SiliconeMT-500SAS Alumina Silica — Tayca Corporation Silicone MT-500H Alumina —Tayca Corporation MT-100AQ Silica — Tayca Corporation Aluminum hydroxideAlginic acid Eusolex T Water — Merck KgaA Simethicone Eusolex T-2000Alumina — Merck KgaA Simethicone Eusolex T-Olio F Silica C₁₂₋₁₅ MerckKgaA Dimethylsilate Alkylbenzoate Water Calcium Poly- hydroxystearateSilica Dimethylsilate Eusolex T-Olio P Water Octyl Palmitate Merck KgaASimethicone PEG-7 Hydrogenated Castor Oil Sorbitan Oleate HydrogenatedCastor Oil Beeswax Stearic acid Eusolex T-Aqua Water AluminaPhenoxyethanol Merck KgaA Sodium Sodium metaphosphate MethylparabensSodium metaphosphate Eusolex T-45D Alumina Isononyl Merck KgaASimethicone Isononanuate Polyglyceryl Ricinoleate Kronos 1171 None —Kronos (Titanium dioxide 171) Titanium dioxide P25 None — DegussaTitanium dioxide Octyltri- — Degussa T805 methylsilane (Uvinul TiO₂)UV-Titan X610 Alumina — Kemira Dimethicone UV-Titan X170 Alumina —Kemira Dimethicone UV-Titan X161 Alumina Silica — Kemira Stearic acidUV-Titan M210 Alumina — Kemira UV-Titan M212 Alumina Glycerol KemiraUV-Titan M262 Alumina — Kemira Silicone UV-Titan M160 Alumina Silica —Kemira Stearic acid Tioveil AQ 10PG Alumina Silica Water PropyleneSolaveil Uniquema glycol Mirasun TiW 60 Alumina Silica WaterRhone-Poulenc

The titanium dioxides of the invention are distinguished by a primaryparticle size between 10 nm to 150 nm.

Titanium dioxides particularly preferred for the purposes of the presentinvention are MT-100 Z and MT-100 TV from Tayca Corporation, EusolexT-2000 from Merck and titanium dioxide T 805 from Degussa.

Further advantageous pigments are latex particles. Latex particles whichare advantageous according to the invention are described in thefollowing publications: U.S. Pat. No. 5,663,213 and EP 0 761 201.Particularly advantageous latex particles are those formed from waterand styrene/acrylate copolymers and available for example under theproprietary name “Alliance SunSphere” from Rohm & Haas.

An advantageous organic pigment for the purposes of the presentinvention is2,2′-methylenebis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl-)phenol)(INCI: bis-octyltriazol), which is obtainable under the proprietary nameTinosorb® M from CIBA-Chemikalien GmbH.

It is particularly advantageous for the purposes of the presentinvention for particulate UV filter substances which are not already inthe form of a predispersion first to be dispersed in one or more dialkylnaphthalates of the invention and for this basic dispersion then to befurther processed. Whereas auxiliaries which may enter into unwantedinteractions with other substances of the cosmetic or dermatologicalformulation are usually added for stabilization to commerciallyavailable predispersions, it is astonishingly possible to dispense withthe addition of such stabilizers when preparing basic dispersions of theinvention.

The total amount of one or more water-soluble UV filter substances inthe finished cosmetic or dermatological preparations is advantageouslychosen from the range 0.01% by weight to 20% by weight, preferably from0.1 to 10% by weight, in each case based on the total weight of thepreparations.

In accordance with still another important embodiment, an alkoxycryleneof formula (I) is combined in a sunscreen or dermatological formulationwith asymmetrically substituted triazine UV filter compounds and/or abroad-band filter compound and optionally, but preferably, together witha dibenzoylmethane derivative.

Asymmetrically substituted triazine derivatives display a good lightprotection effect. Their main disadvantage is, however, that theirsolubility is low in conventional oil components. Well-known solventscan dissolve only up to a maximum of 15% by weight of these compounds,which usually corresponds to a concentration of about 1 to 1.5% byweight of dissolved (=active) filter substance in the complete cosmeticor dermatological preparation.

One disadvantage of the prior art is accordingly that generally onlycomparatively low sun protection factors have been achievable with thesefilter substances because their solubility or dispersibility in theformulations is too low, i.e. they can be satisfactorily incorporatedinto such formulations only with difficulty or not at all.

Even if it is also possible in principle to achieve a certain UVprotection when the solubility is limited, another problem frequentlyoccurs, that is recrystallization. Substances of low solubility inparticular recrystallize comparatively rapidly, which may be induced byfluctuations in temperature or other influences. Uncontrolledrecrystallization of an essential ingredient of a preparation such as aUV filter has, however, extremely disadvantageous effects on theproperties of the given preparation and, not least, on the desired lightprotection.

It was an object of the present invention to obtain in a simple mannerpreparations which are distinguished by an increased content ofasymmetrically substituted triazine derivatives and a correspondinglyhigh sun protection factor.

Disadvantages of the prior art are remedied by active ingredientcombinations effective for light protection and composed of:

(a) one or more UV filter substances selected from the group ofasymmetrically substituted triazine derivatives, and(b) one or more alkoxycrylenes having the structural formula (I); and(c) optionally a dibenzoylmethane derivative and/or a dialkylnaphthalate.

Advantageous asymmetrically substituted s-triazine derivatives withinthe meaning of this embodiment of the present invention are, forexample, those described in EP-A-570 838, whose chemical structure isrepresented by the generic formula

whereR is a branched or unbranched C₁-C₁₈-alkyl radical, a C₅-C₁₂-cycloalkylradical, optionally substituted by one or more C₁-C₄-alkyl groups, andX is an oxygen atom or an NH group,R₁ is a branched or unbranched C₁-C₁₈-alkyl radical, a C₅-C₁₂-cycloalkylradical, optionally substituted by one or more C₁-C₄-alkyl groups, or ahydrogen atom, an alkali metal atom, an ammonium group or a group of theformula

in whichA is a branched or unbranched C₁-C₁₈-alkyl radical, a C₅-C₁₂-cycloalkylor aryl radical, optionally substituted by one or more C₁-C₄-alkylgroups,R₃ is a hydrogen atom or a methyl group,n is a number from 1 to 10,R₂ is a branched or unbranched C₁-C₁₈-alkyl radical, a C₅-C₁₂-cycloalkylradical, optionally substituted by one or more C₁-C₄-alkyl groups, andif X is the NH group,a branched or unbranched C₁-C₁₈-alkyl radical, a C₅-C₁₂-cycloalkylradical, optionally substituted by one or more C₁-C₄-alkyl groups, or ahydrogen atom, an alkali metal atom, an ammonium group or a group of theformula

in whichA is a branched or unbranched C₁-C₁₈-alkyl radical, a C₅-C₁₂-cycloalkylor aryl radical, optionally substituted by one or more C₁-C₄-alkylgroups,R₃ is a hydrogen atom or a methyl group,n is a number from 1 to 10, if X is an oxygen atom.

In a preferred form of this triazine embodiment, the compositions aresunscreen, cosmetic or dermatological formulations that include acontent of least one asymmetrically substituted s-triazine selected fromthe group of substances having the following structural formula:

All the bisresorcinyltriazines, are advantageous for this embodiment ofthe purpose of the present invention. R₄ and R₅ are very particularlyadvantageously selected from the group of branched or unbranched alkylgroups of 1 to 18 carbon atoms. The alkyl groups may also againadvantageously be substituted by silyloxy groups.

A₁ is advantageously a substituted homocyclic or heterocyclic aromaticfive-membered ring or six-membered ring.

The following compounds are very particularly advantageous:

where R₆ is a hydrogen atom or a branched or unbranched alkyl group with1 to 10 carbon atoms, in particular2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine(INCI: aniso triazine), which is obtainable under the proprietary nameTinosorb® S from CIBA-Chemikalien GmbH and is characterized by thefollowing structure:

Also advantageous is2,4-bis{[4-(3-sulfonato-2-hydroxypropyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine sodium salt, which is characterized by thefollowing structure:

Also advantageous is2,4-bis{[4-(3-(2-propyloxy)-2-hydroxypropyloxy)-2-hydroxy]phenyl}-6(4-methoxyphenyl)-1,3,5-triazine,which is characterized by the following structure:

Also advantageous is2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-[4-(2-methoxyethoxycarbonyl)phenylamino]-1,3,5-triazine, which is characterized by the followingstructure:

Also advantageous is2,4-bis{[4-(3-(2-propyloxy)-2-hydroxypropyloxy)-2-hydroxy]phenyl}-6-[4-(ethoxycarbonyl)phenylamino]-1,3,5-triazinewhich is characterized by the following structure:

Also advantageous is2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(1-methylpyrrol-2-yl)1,3,5-triazine, which is characterized by the following structure:

Also advantageous is2,4-bis{[4-tris(trimethylsiloxysilylpropyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine,which is characterized by the following structure:

Also advantageous is2,4-bis{[4-(2-methylpropenyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine,which is characterized by the following structure:

Also advantageous is2,4-bis{[4-(1′,1′,1′,3′,5′,5′,5′-heptamethylsiloxy-2-methylpropyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine,which is characterized by the following structure:

In a particularly preferred embodiment, the present invention relates tocosmetic or dermatological formulations with a content of anasymmetrically substituted s-triazine whose chemical structure isrepresented by the formula

which is also referred to hereinafter as dioctylbutylamidotriazone(INCI) and is obtainable under the proprietary name UVASORB HEB fromSigma 3 V.

The asymmetrically substituted s-triazine derivative(s) of the inventionare advantageously incorporated into the oil phase of the cosmetic ordermatological formulations.

The total amount of one or more asymmetrically substituted s-triazinederivatives, in particular of dioctylbutylamidotriazone, in the finishedcosmetic or dermatological preparations is advantageously chosen fromthe range from 0.1 to 15.0% by weight, preferably 0.5 to 10.0% byweight, based on the total weight of the preparations.

The cosmetic or dermatological light protection formulations of theinvention may have conventional compositions when used for cosmetic ordermatological light protection and for the treatment, care andcleansing of skin and/or the hair and as a make-up product in decorativecosmetics.

In accordance with one important embodiment, an alkoxycrylene of formula(I) is combined in a sunscreen or dermatological formulation with alipophilic oxidation or UV-sensitive active ingredients, such asretinoic acid and its derivatives, e.g., tretinoin or isotretinoinand/or a broad-band filter compound and optionally, but preferably,together with a dibenzoylmethane derivative.

Advantageous lipophilic active ingredients which are stabilized in anexcellent manner by the use according to the invention are those whoselog P value is greater than 3.5. P is the partition coefficient, whichis defined as the ratio of the equilibrium concentration of a dissolvedsubstance in a two-phase system which consists of two solvents which areessentially immiscible with one another. These two solvents are, in thepresent case, n-octanol and water, i.e.

$P_{ow} = \frac{C_{n - {octanol}}}{C_{water}}$

It is advantageous for the purposes of the present invention to choosethe lipophilic active ingredients from the group of ubiquinones andplastoquinones. For the purposes of the present invention, coenzyme Q10,which has a log P value of about 15, is very particularly advantageous.

It was particularly surprising that very advantageous preparationsaccording to the present invention can be obtained when the activeingredient(s) is/are chosen only from the group of ubiquinones.

Further lipophilic active ingredients which are advantageous accordingto the invention are retinoids (vitamin A acid and/or derivativesthereof) or vitamin A and/or derivatives thereof. The group of retinoidsadvantageous according to the invention is defined as including allcosmetically and/or pharmaceutically acceptable retinoids, includingretinol and its esters, retinal and also retinoic acid (vitamin A acid)and esters thereof. For the purposes of the present invention, retinol(with a log P value of about 7) and retinyl palmitate (with a log Pvalue of about 13) are particularly advantageous.

It was also particularly surprising that very advantageous preparationscan be obtained according to the present invention when the activeingredient(s) is/are chosen only from the group of retinoids.

Further lipophilic acid ingredients advantageous according to theinvention are carotenoids. For the purposes of the present invention,.beta.-carotene, which has a log P value of 15, for example, isparticularly advantageous.

Further lipophilic active ingredients advantageous according to theinvention are: lipoic acid and derivatives, vitamin E and derivatives,vitamin F, dioic acid [8-hexadecene-1,16-dicarboxylic acid (CAS number20701-68-2)]

The amount of lipophilic active ingredients (one or more compounds) inthe preparations is preferably 0.0001 to 10% by weight, particularlypreferably 0.001 to 5% by weight, based on the total weight of thepreparation.

Synthesis of methyl or ethyl2-cyano-3-(4′-methoxyphenyl)-3-phenylpropenoate (Methyl or EthylMethoxycrylene or Methyl or Ethyl MeOcrylene)

4-Methoxy benzophenone (MW=182.22 g/mole; 500 g; 2.74 mole; 1 moleequivalence) and methyl cyanoacetate (MW=99.09 g/mole; 367.06 g; 3.70mole; 1.35 mole equivalence) were placed in 1-L 3-neck flask assembledwith mechanical stirrer and nitrogen inlet, which provided continuousflow of nitrogen through the reaction mixture (nitrogen is bubbledthrough the reaction mixture). Next, toluene (1200 ml) and acetic acid(240 ml; ratio of toluene/acetic acid=5/1) are added to the flaskfollowed by ammonium acetate (MW=77.09 g/mole; 21.12 g; 0.274 mole, 0.1mole equivalence; the catalyst is added 4 times this amount duringreaction time). The flask is then assembled with Dean-Stark receiverthrough which reaction water is being continuously removed.

Comments:

-   -   1. Aliquots of the reaction mixture are taken to check the rate        of completion of the reaction.    -   2. The amount of water expected from this reaction is 49.5 ml.        However, I collected about 120 ml of water phase. This is due to        the fact that the water is distilled in form of a mixture,        water/acetic acid/toluene.    -   3. To prevent from loosing the methyl acetate from the reaction        mixture, it helps to put a short packed column between        Dean-Stark receiver and the flask.

Work-Up:

The reaction mixture is cooled to room temperature and ethyl acetate isadded to dissolve all solids before the crude mixture is washed severaltime with water, to remove acetic acid and salts. The solvents are thenremoved from the reaction mixture by distillation. The crude solidproduct is re-crystallized from hot methanol (or toluene/methanolmixture, if such is preferred).

Comments:

The finished product begins to crystallize out from the cooling reactionmixture and thus can be filtered off, but it still is very acidic, sothe crystals ought to be washed with water/methanol mixture to wash outany acetic acid and salts residues. Thus obtained the product then canbe re-crystallized and the mother liquor can be washed with water,dried, and second crop of the product can be obtained.

Synthesis of Alkyl 2-cyano-3-(4′-methoxyphenyl)-3-phenylpropenoate:

Reaction Procedure:

Methyl (or ethyl) 2-cyano-3-(4′-methoxyphenyl)-3-phenylpropenoate (900g, 3.06 mole; MW=293.32), alkyl alcohol (3.84 mole; 1.25 moleequivalence), and Tegokat 250 (0.03% of total batch weight) were placedin 2 L 3-neck round-bottom flask and heated to temperature set at 185 C(365 F), with nitrogen purging it well to remove forming methanol (orethanol) via the simple distillation setup with packed column.After 3 h, GC showed full conversion of methyl2-cyano-3-(4′-methoxyphenyl)-3-phenylpropenoate to the desired product.

Work-Up:

The unreacted alkyl alcohol was completely removed by vacuumdistillation. Temperature of the reaction was lowered to 110 C (230 F)and calculated amount (2% of total batch weight) of the SSP (tinremoving agent) was added. The product was stirred at this temperaturefor 2 hours and then filtered hot. Small amount of celite was addedright before filtration to enhance the filtration—with celite thefiltration was more efficient and faster.

Results:

Yield of the product 94% of stoichiometric amount Purity of finishedproduct 99.81% (area count, GC).

EXAMPLES

The following compositions (Table I) were prepared according to theprocedure indicated in order to show the surprisingly superiorphotostabilizing effect on avobenzone of the alkoxycrylenes (4.5 wt. %)described herein in comparison to an equimolar amount (2.75 wt. %) ofoctocrylene. The compound described as “methoxycrylene” had thefollowing formula (IV):

TABLE 1 COMPOSITIONS OF FORMULATIONS TESTED FOR PHOTOSTABILITY Example 1Example 2 Example 3 # Ingredients (4.5% C20 Methoxycrylene) (POS: 2.75%OC Only) (NEG: No Photostabilizer) Oil Phase Ingredients  1 Avobenzone3.00% 3.00% 3.00%  2 Octisalate 5.00% 5.00% 5.00%  3 Homosalate 7.50%7.50% 7.50%  4 Benzophenone-3 0.49% 0.49% 0.49%  5 Octocrylene*** (OC)0.00% 2.75% 0.00%  6 C20 Methoxycrylene*** (C20MC) 4.50% 0.00% 0.00%  7Phenylethyl benzoate 0.00% 0.00% 2.75%  8 Dimethicone (350 cSt) 1.25%1.25% 1.25%  9 Methyl trimethicone 0.00% 1.75% 1.75% 10 VP/Eicosenecopolymer 1.00% 1.00% 1.00% 11 Cetearyl alcohol 0.36% 0.36% 0.36% TotalOil Ingredients 23.10% 23.10% 23.10% Emulsifiers 12 Steareth-21 0.80%0.80% 0.80% 13 Steareth-2 0.60% 0.60% 0.60% 14 Potassium cetyl phosphate& 3.00% 3.00% 3.00% Hydrogenated palm glycerides Total Emulsifiers 4.40%4.40% 4.40% x Water Phase Ingredients 15 Disodium EDTA 0.10% 0.10% 0.10%16 Glycerin 4.00% 4.00% 4.00% 17 Benzyl alcohol 1.00% 1.00% 1.00% 18Methylparaben 0.10% 0.10% 0.10% 19 Propylparaben 0.05% 0.05% 0.05% 20Water 62.25% 62.25% 62.25% Total Water Ingredients 67.50% 67.50% 67.50%Other Ingredients 21 Acrylamide/Sodium acryloyldimethyl 2.50% 2.50%2.50% taurate copolymer 22 Aluminum starch octenyl succinate 2.50% 2.50%2.50% Total Other Ingredients 5.00% 35.00% 5.00% Total 100.00% 100.00%100.00% **Reported as Coefficients of Variation on report generated byLabsphere instrument ***On a molar basis, 4.5% C20 methoxycrylene isequal to 2.75% Octocrylene PROCEDURE 1. Charge secondary vessel with1-7. With stirring, heat to 90° C. Add in order 10-14. Continue stirringuntil homogeneous. 2. Charged primary vessel with water (20). Withstirring, ad 15-16. Heat to 90° C. 3. Add oil phase (1-7, 10-14) towater phase (20, 15, 16). Stir vigorously for 10 minutes. Switch tohomomixer and homogenize until temperature is below 55 4. Whentemperature of emulsion is below 55° C., switch to sweep stirring.Preblend 17-19. Add to emulsion when temperature is below 45° C. 5. Add21 and continue sweep stirring as emulsion thickens. When smooth, add22. Pre-blend 8 and 9 and add to batch. 6. Q.S. water and package whentemperature of batch is less than 35° C.

The surprising photostability of the sunscreen composition of Example 1,Table I, including methoxycrylene, in comparison to the octocrylene ofthe prior art, is shown in FIG. 1, which is a graph of the data ofExamples 1 through 3, above, and in the following SPF reports forExamples 4-6.

TABLE 2 Example 4 Example 5 Example 6 Results of Irradiation with 35 MED(7% Ethylhexyl methoxycrylene) (0% Ethylhexyl methoxycrylene) 8.8%Octocrylene) Loss of UVA protection** −18.26% −80.47% −55.96% Loss ofUVB protection** −6.46% −52.01% −4.51% Loss of SPF** −7.43% −70.42%−16.00% **Reported as Coefficients of Variation on report generated byLabsphere instrument software. COMPOSITIONS OF FORMULATIONS TESTED FORPHOTOSTABILITY CAB6-057 CAB6-058 CAB6-060 # Ingredients (7% Ethylhexylmethoxycrylene) (0% Ethylhexyl methoxycrylene) (0% Ethylhexylmethoxycrylene) Oil Phase Ingredients  1 Avobenzone 2.00% 2.00% 2.00%  2Octyl methoxycinnamate (OMC) 5.00% 5.00% 5.00%  3 Phenylethyl benzoate7.50% 7.50% 7.50%  4 Benzophenone-3 0.49% 0.49% 0.49%  5 Octocrylene1.80% 1.80% 8.80%  6 Ethylhexyl methoxycrylene*** 7.00% 0.00% 0.00%  7Polyisobutene 0.00% 7.00% 0.00% Total Oil Ingredients 23.79% 23.79%23.79% Emulsifier  8 Acrylates/C10-30 alkyl acrylate 0.25% 0.25% 0.25%crosspolymer  9 Sorbitan laurate 0.20% 0.20% 0.20% Total Emulsifiers0.45% 0.45% 0.45% x Water Phase Ingredients 10 Disodium EDTA 0.10% 0.10%0.10% 11 Cetyl hydroxyethylcellulose 0.30% 0.30% 0.30% 12 Glycerin 4.00%4.00% 4.00% 13 Benzyl alcohol 1.00% 1.00% 1.00% 14 Methylparaben 0.10%0.10% 0.10% 15 Propylparaben 0.05% 0.05% 0.05% 16 Triethanolamine 0.40%0.40% 0.40% 17 Water 69.81% 69.81% 69.81% Total Water Ingredients 75.76%75.76% 75.76% Total 100.00% 100.00% 100.00% PROCEDURE 1. Charge primaryvessel with water (16). Dissolve 10. Heatto 85 degrees C. Disperse 11.Remove from heat. Continue stirring until 11 is fully dissolved. 2. Insecondary vessel, add 2-7 and 9 with stirring. Add 1 and heat to 45degrees C. Continue stirring until solution is clear. 3. Add 8 to oiland stir until completely incorporated. 4. When oil phase and waterphase are 45 degrees C., add oil (1-7, 8, 9) to water (17, 10, 11).Maintain temperature and stir for 30 minutes. 5. Remove batch from heat.Preblend 12 and 16. Add to batch with stirring. Increase agitation asbatch thickens. 6. Preblend 13-15, making sure that 14 and 15 arecompletely dissolved. Add to batch. Q.S. water and package whentemperature of batch is less than 35° C.

Additional alkoxycrylene molecules were tested in accordance with theprocedure indicated in Table 2, wherein radical R₃ of the alkoxycryleneof formula (I) has an R₃=ethyl hexyl (formula IV):

The data for the sunscreen composition of Example 4 is shown in thegraph of FIG. 2 and the data for the composition of Example 5 is shownin the graph of FIG. 3. For Examples 4-6, the data of Example 6 (shownin graph form as FIG. 4) compares 7% ethylhexyl methoxycrylene (formulaV) and 1.8% octocrylene (Example 4) to 8.8% octocrylene with noalkoxycrylene. As shown in the graph of FIG. 4 and the following SPFreports for Examples 4-6, the alkoxy crylenes described herein areunexpectedly better photostabilizers than octocrylene.

SPF REPORT Sample: Example 4 UV Photostability Comment: 0, 35 MEDWavelength Range: 290-400 nm Units: SPF T(UVA) T(UVB) # of Scans: 2 2 2Mean: 24.67 4.52% 5.43% STD: 1.83 0.83% 0.35% COV: 7.43% 18.26% 6.46%UVA/UVB Ratio: 1.1 Boots Star Rating: N/A less than 5 Scans Scan # SPFCritical Wavelength 1 25.97 385 2 23.37 384 Sample: Example 5 UVPhotostability Comment: 0, 35 MED Wavelength Range: 290-400 nm Units:SPF T(UVA) T(UVB) # of Scans: 2 2 2 Mean: 16.76 23.10% 8.07% STD: 11.818.59% 4.20% COV: 70.42% 80.47% 52.01% UVA/UVB Ratio: 0.72 Boots StarRating: N/A less than 5 Scans Scan # SPF Critical Wavelength 1 25.11 3802 8.41 372 Sample: Example 6 UV Photostability Comment: 0, 35 MEDWavelength Range: 290-400 nm Units: SPF T(UVA) T(UVB) # of Scans: 2 2 2Mean: 23.83 11.80% 5.27% STD: 3.81 6.61% 0.24% COV: 16.00% 55.96% 4.51%UVA/UVB Ratio: 0.88 Boots Star Rating: N/A less than 5 Scans Scan # SPFCritical Wavelength 1 26.52 382 2 21.13 375

As shown in the above-referenced formulations and data of Examples 4-6,the combination of avobenzone (UVA) with octylmethoxycinnamate (UVB) hasparticularly surprising results when combined with a stabilizing amountof an alkoxycrylene of formula I. It is well know that octocrylenestabilizes octyl methoxycinnamate (OMC), a UVB filter, but does notphotostabilizer avobenzone, a UVA filter. In accordance with thecompositions and methods described herein, it has been found that thealkoxycrylene of formula I photostabilize octyl methyoxycinnemate (OMC)much better than OMC, and also photostabilizes avobenzone. Thealkoxycrylenes, therefore, can photostabilize sunscreen compositions.Accordingly, by adding an alkoxycrylene, both avobenzone and OMC can bephotostabilized by the alkoxycrylene.

Example 4 (7% alkoxycrylene and 1.8% octocrylene) loses only 18.26% UVA;6.46% UVB; and 7.43% of its SPM when subjected to 35 MED irradiation.The same formulation containing no alkoxycrylene (Example 5) loses80.47% UVA; 52.01% UVB; and 70.42% of its SPF. Example 6, containing8.8% octocrylene and no alkoxycrylene loses 55.96% UVA; 4.51% UVB(octocrylene photostabilizes OMC but not avobenzone); and 16% of itsSPF, Examples 4, 5 and 6 are shown graphically in FIGS. 2, 3 and 4.

Additional sunscreen compositions were prepared containing 0 wt. %, 3wt. % and 5 wt. % 2-ethylhexyl methoxycrylene, as shown in Examples 7-10in Table 3:

TABLE 3 Example 7 Example 8 Example 9 Example 10 (5% 2-EH (3% 2-EH (0%2-EH (3% 2-EH # Ingredients Methoxycrylene) methoxycrylene)methoxycrylene methoxycrylene) Oil Phase Ingredients  1 Avobenzone 3.00%3.00% 3.00% 3.00%  2 Octisalate 5.00% 5.00% 5.00% 5.00%  3 Octinoxate(Octyl methoxycinnamate or OMC or 7.50% 7.50% 7.50% 7.50% MCX)  4Benzophenone-3 0.49% 0.49% 0.49% 0.49%  5 Octocrylene*** (OC) 5.00%7.00% 10.00% 10.00%  6 Ethylhexyl methoxycrylene*** (2-EH 5.00% 3.00%0.00% 3.00% methoxycrylene or MOC)  7 Cetearyl alcohol 0.35% 0.35% 0.35%0.35%  8 C30-38 Olefin/Isopropyl maleate/MA copolymer 0.80% 0.80% 0.80%0.80% Total Oil Ingredients 27.14% 27.14% 27.14% 30.14% Emulsifiers  9Steareth-21 0.45% 0.45% 0.00% 0.00% 10 Steareth-2 0.65% 0.65% 0.00%0.00% 11 Glyceryl stearate/PEG-100 stearate 0.00% 0.00% 1.00% 1.00% 12Potassium cetyl phosphate & Hydrogenated palm 3.00% 3.00% 3.00% 3.00%glycerides Total Emulsifiers 4.10% 4.10% 4.00% 4.00% x Water PhaseIngredients 13 Disodium EDTA 0.10% 0.10% 0.10% 0.10% 14 Tromethamine0.04% 0.04% 0.04% 0.04% 15 Glycerin 4.00% 4.00% 4.00% 4.00% 16 Benzylalcohol 1.00% 1.00% 1.00% 1.00% 17 Methylparaben 0.10% 0.10% 0.10% 0.10%18 Propylparaben 0.05% 0.05% 0.05% 0.05% 19 Water 58.47% 58.47% 58.57%55.57% Total Water Ingredients 63.76% 63.76% 63.86% 60.86% OtherIngredients 20 Acrylamide/Sodium acryloyldimethyltaurate copolymer (and)Isohexadecane (and) Polysorbate 80 2.00% 2.00% 2.00% 2.00% 21 Aluminumstarch octenyl succinate 3.00% 3.00% 3.00% 3.00% Total Other Ingredients5.00% 5.00% 5.00% 5.00% Total 100.00% 100.00% 100.00% 100.00%PROCEDURE 1. Charge secondary vessel with 1-9. With stirring, heat to90° C. Add in order 9-12. Continue stirring until homogeneous. 2.Charged primary vessel with water (19). With stirring, add 14-15. Heatto 90° C. 3. Add oil phase (1-8, 9-12) to water phase (19, 14, 15). Stirvigorously for 10 minutes. Switch to homomixer and homogenize untiltemperature is below 60° C. 4. When temperature of emulsion is below 60°C., switch to sweep stirring. Preblend 15-18. Add to emulsion whentemperature is below 45° C. 5. Add 20 and continue sweep stirring asemulsion thickens. When smooth, add 21. 6. Q.S. water and package whentemperature of batch is less than 35° C. Q.S. = quantity sufficient

The results were as follows and clearly show that adding morealkoxycrylene to sunscreen formulation provides more Photostabilizationof both UVA and UVB filters. Example 7, having the most MOC (5%) and theleast OC (5%) provided the best results.

Example 7 Example 8 Example 9 Example 10 Results of Irradiation with 20MED 5% OC/5% MOC 7% OC/3% MOC 10% OC/0% MOC 10% OC/3% MOC UVA1/UV ratiobefore UV irradiation 0.84 0.83 0.79 0.83 UVA1/UV ratio after 20 MED0.76 0.71 0.54 0.70 Difference after irradiation 0.09 0.12 0.25 0.13 %change 10.00% 15.00% 32.00% 16.00% OC = Octocrylene; MOC = EthylhexylMethoxycrylene; UVA1 = total area under curve from 340 to 400 nm; UV =total area under curve from 290 to 400 nm

More sunscreen compositions were prepared containing 0, 2, 4 and 6 wt. %2-ethylhexyl methoxycrylene to test the photostabilizing capacity of themethoxycrylenes to photostabilize avobenzone and other photodegradableUV-absorbers, as shown in Examples 11-14 in Table 4:

TABLE 4 Example 11 Example 12 Example 13 Example 14 # Ingredients 0% MOC2% MOC 4% MOC 6% MOC Oil Phase Ingredients  1 Avobenzone 3.00% 3.00%3.00% 3.00%  2 Octisalate 5.00% 5.00% 5.00% 5.00%  3 Homosalate 7.50%7.50% 7.50% 7.50%  4 Butyloctyl benzoate 9.00% 7.00% 5.00% 3.00%  5Ethylhexyl methoxycrylene*** (2-EH methoxycrylene 0.00% 2.00% 4.00%6.00% or MOC)  6 Cetearyl alcohol 0.35% 0.35% 0.35% 0.35%  7 VP/Eicosenecopolymer 1.00% 1.00% 1.00% 1.00% Total Oil Ingredients 25.85% 25.85%25.85% 25.85% Emulsifiers  8 Steareth-21 0.00% 0.00% 0.00% 0.00%  9Steareth-2 0.00% 0.00% 0.00% 0.00% 10 Glyceryl stearate/PEG-100 stearate1.00% 1.00% 1.00% 1.00% 11 Potassium cetyl phosphate & Hydrogenated palmglycerides 3.00% 3.00% 3.00% 3.00% Total Emulsifiers 4.00% 4.00% 4.00%4.00% x Water Phase Ingredients 12 Disodium EDTA 0.10% 0.10% 0.10% 0.10%13 Glycerin 4.00% 4.00% 4.00% 4.00% 14 Benzyl alcohol 1.00% 1.00% 1.00%1.00% 15 Methylparaben 0.10% 0.10% 0.10% 0.10% 16 Propylparaben 0.05%0.05% 0.05% 0.05% 17 Water 59.90% 59.90% 59.90% 59.90% Total WaterIngredients 65.15% 65.15% 65.15% 65.15% Other Ingredients 18Acrylamide/Sodium acryloyldimethyltaurate copolymer (and) Isohexadecane(and) Polysorbate 80 2.00% 2.00% 2.00% 2.00% 19 Aluminum starch octenylsuccinate 3.00% 3.00% 3.00% 3.00% Total Other Ingredients 5.00% 5.00%5.00% 5.00% Total 100.00% 100.00% 100.00% 100.00% PROCEDURE 1. Chargesecondary vessel with 1-7. With stirring, heat to 90° C. Add in order10-11. Continue stirring until homogeneous. 2. Charged primary vesselwith water (17). With stirring, add 12. Heat to 90° C. 3. Add oil phase(1-7, 10-11) to water phase (17, 12). Stir vigorously for 10 minutes.Switch to homomixer and homogenize until temperature is below 60° C. 4.When temperature of emulsion is below 60° C., switch to sweep stirring.Preblend 13-16. Add to emulsion when temperature is below 45° C. 5. Add18 and continue sweep stirring as emulsion thickens. When smooth, add19. 6. Q.S. water and package when temperature of batch is less than 35°C. Q.S. = quantity sufficient

The results were as follows:

Example 11 Example 12 Example 13 Example 14 Results of Irradiation with20 MED 0% MOC 2% MOC 4% MOC 6% MOC UVA1/UV ratio before UV irradiation0.88 0.91 0.90 0.91 UVA1/UV ratio after 20 MED 0.32 0.85 0.88 0.90Difference after irradiation 0.56 0.06 0.02 0.01 % change 63.67% 6.43%2.00% 1.04% MOC = Ethylhexyl Methoxycrylene; UVA1 = total area undercurve from 340 to 400 nm; UV = total area under curve from 290 to 400 nm

It should be noted that the sunscreen formulations of Examples 11-14contain no octyl methoxycinnemate or other photostabilizers. It is clearfrom the data of Examples 11-14 that the alkoxycrylene of formula Iphotostabilize avobenzone and other dibenzoylmethane derivatives withsurprising efficacy.

Additional sunscreen compositions were prepared containing 5 wt. %2-ethylhexyl methoxycrylene with and without 1.5 wt. % Tinosorb S orTinosorb M, as shown in Examples 15 and 16 in Table 5:

TABLE 5 Example 15 Example 16 1.5% Bemotrizinol/5% 5% Bisoctrizole/5% #Ingredients MOC MOC Oil Phase Ingredients 1 Avobenzone 3.00% 3.00% 2Octisalate 5.00% 5.00% 3 Octinoxate (Octyl methoxycinnamate or OMC orMCX) 7.50% 7.50% 4 Bemotrizinol (Tinosorb S) 1.50% 0.00% 6 Ethylhexylmethoxycrylene*** (2-EH methoxycrylene or MOC) 5.00% 5.00% 7Trideceth-12 1.00% 1.00% 8 VP/Eicosene copolymer 1.00% 1.00% 9 Behenylalcohol + Glyceryl stearate + Glyceryl stearate citrate + Sodiumdicocoylethylenediamine PEG-15 sulfate 1.00% 1.00% Total Oil Ingredients25.00% 23.50% Emulsifiers (See 7, 9, 12) 0.00% 0.00% Total Emulsifiers0.00% 0.00% x Water Phase Ingredients 10 Disodium EDTA 0.10% 0.10% 11Xanthan gum 0.10% 0.10% 12 Sodium dicocoylethylenediamine PEG-15sulfate + Sodium lauroyl 1.00% 1.00% lactylate 13 Glycerin 4.00% 4.00%14 Benzyl alcohol 1.00% 1.00% 15 Methylparaben 0.10% 0.10% 16Propylparaben 0.05% 0.05% 17 Water 63.65% 60.15% Total Water Ingredients70.00% 66.50% Other Ingredients 18 Bisoctrizole (Tinosorb M) 0.00% 5.00%19 Acrylamide/Sodium acryloyldimethyltaurate copolymer (and)Isohexadecane (and) Polysorbate 80 2.00% 2.00% 20 Aluminum starchoctenyl succinate 3.00% 3.00% Total Other Ingredients 5.00% 10.00% Total100.00% 100.00% PROCEDURE 1. Charge secondary vessel with 1-9. Withstirring, heat to 70° C. Continue stirring until homogeneous. Maintaintemperature. 2. Charged a third vessel with water (19). Dissolve 10 withstirring. Add 11 and stir until Xanthan gum is completely dissolved. 3.Place ⅓ of (2) in primary vessel. Heat to 65° C. Add 12 and stir untilhomogeneous. 4. Add oil phase (1-9) to water (10-12) in primary vessel.Homogenize for two minutes, or until emulsion is fully formed. 5. Removebatch from heat. Slowly add balance of water (see Step 2) to emulsionwith stirring. Stir while cooling. 6. Preblend 13-16. Add to batch withstirring. Add 18 to batch with stirring. 7. Add 19 and stir until smoothand homogeneous. Add 20 and stir until fully incorporated. Q.S. water.Package when batch is < 35° C. Q.S. = quantity sufficient

The results were as follows:

Example 15 Example 16 Results of Irradiation with 20 MED 1.5%Bemotrizinol/5% MOC 5% Bisoctrizole/5% MOC UVA1/UV ratio before UVirradiation 0.87 0.87 UVA1/UV ratio after 20 MED 0.81 0.84 Differenceafter irradiation 0.06 0.03 % change 6.66% 3.55% MOC = EthylhexylMethoxycrylene; UVA1 = total area under curve from 340 to 400 nm; UV =total area under curve from 290 to 400 nm

Tinsorb S of Examples 15 and 16 is a known UVA and UVB photostabilizer(more effective in the UVA range) for photostabilizing both avobenzoneand octyl methoxycinnamate. Surprisingly, as shown in the data ofExamples 15 and 16 (both Examples include 5% MOC) omitting the Tinsorb Sfrom Example 16 makes very little difference in photostabilizing thecombination of avobenzone and OMC.

Additional sunscreen formulations were tested containing 5 wt. %butyloctyl methoxycrylene and a triazine derivative (Uvinul T-150); abenzophenone derivative (Uvinul A Plus); and three water soluble UVfilters (Mexonylsx; Neo Heliopan AP; and Neo Heliopan Hydro), as shownin examples 17-21 of table 6:

TABLE 6 FORMULAS THAT ILLUSTRATE PRIOR ART COMBINATIONS Example 17Example 18 Example 19 Example 20 Example 21 2% Uvinul 2% Uvinul 2%Mexoryl 2% Neo Hellopan 2% Neo # Ingredients T-150 A Plus SX AP HellopanHydro Oil Phase Ingredients  1 Avobenzone 3.00% 3.00% 3.00% 3.00% 3.00% 2 Octisalate 5.00% 5.00% 5.00% 5.00% 5.00%  3 Octinoxate (Octylmethoxycinnamate or OMC 7.50% 7.50% 7.50% 7.50% 7.50% or MCX)  4 Octyltriazone (Uvinul T-150, BASF) 2.00% 0.00% 0.00% 0.00% 0.00%  5Diethylamino Hydroxybenzoyl Hexyl Benzoate 0.00% 2.00% 0.00% 0.00% 0.00%(Uvinul A Plus, BASF)  6 Butyloctyl methoxycrylene 5.00% 5.00% 5.00%5.00% 5.00%  7 VP/Eicosene copolymer 1.00% 1.00% 1.00% 1.00% 1.00% TotalOil Ingredients 23.50% 23.50% 21.50% 21.50% 21.50% Emulsifiers  8Stearyl alcohol 1.00% 1.00% 1.00% 1.00% 1.00%  9 Glyceryl stearate 1.00%1.00% 1.00% 1.00% 1.00% 10 Polyglyceryl-3 methyl glucose distearate3.00% 3.00% 3.00% 3.00% 3.00% Total Emulsifiers 5.00% 5.00% 5.00% 5.00%5.00% x Water Phase Ingredients 11 Disodium EDTA 0.10% 0.10% 0.10% 0.10%0.10% 12 Ecamsule neutralized with triethanolamine 0.00% 0.00% 2.00%0.00% 0.00% (Mexoryl SX, Chemex) 13 Bisdisulizole disodium (Neo HeliopanAP, Symrise) 0.00% 0.00% 0.00% 2.00% 0.00% 14 Ensulizole neutralizedwith triethanolamine (Neo 0.00% 0.00% 0.00% 0.00% 2.00% Heliopan Hydro,Symrise) 15 Glycerin 4.00% 4.00% 4.00% 4.00% 4.00% 16 Benzyl alcohol1.00% 1.00% 1.00% 1.00% 1.00% 17 Methylparaben 0.10% 0.10% 0.10% 0.10%0.10% 18 Propylparaben 0.05% 0.05% 0.05% 0.05% 0.05% 19 Water 61.25%61.25% 61.25% 61.25% 61.25% Total Water Ingredients 66.50% 66.50% 68.50%68.50% 68.50% Other Ingredients 20 Acrylamide/Sodiumacryloyldimethyltaurate 2.00% 2.00% 2.00% 2.00% 2.00% copolymer (and)Isohexadecane (and) Polysorbate 80 21 Aluminum starch octenyl succinate3.00% 3.00% 3.00% 3.00% 3.00% Total Other Ingredients 5.00% 5.00% 5.00%5.00% 5.00% Total 100.00% 100.00% 100.00% 100.00% 100.00% PROCEDURE 1.Charge secondary vessel with 1-7 . . . With stirring, heat to 80° C. Add8-10. Continue stirring until homogeneous. 2. In another secondaryvessel, dissolve 12 or 13 or 14 in water and set aside. 3. Chargedprimary vessel with water (19), except amount necessary for Step 2 . . .Dissolve 11. Heat to 80° C. 4. Add oil (1-10) to water (11, 19) withstirring. Remove from heat. Homogenize for 10 minutes. Stir whilecooling. 5. When temperature is below 45° C., add pre-mixed 15-18. 6.Add pre-dissolved 12, 13, or 14. 7. Add 20 and continue sweep stirringas emulsion thickens. When smooth, add 21. 8. Q.S. water and packagewhen temperature of batch is less than 35° C. Q.S. = quantity sufficient

Two more sunscreen formulations (Examples 22 and 23) were prepared eachcontaining butyloctyl methoxycrylene, and Example 23 also containingTinosorb® S and Tinosorb® M. As shown in the results, the combination ofan alkoxycrylene, together with a dibenzoylmethane derivative, acinnamate ester, Tinasorb® S and Tinasorb® M, avobenzone and octylmethoxycinnamate is particularly photostable:

Example 22 Example 23 % TinS/0% TinM/7% BMO % TinS/5% TinM/5% BMOCResults of Irradiation with 20 MED UVA1/UV ratio before UV irradiation0.84 0.85 UVA1/UV ratio after 20 MED 0.78 0.83 Difference afterirradiation 0.06 0.02 % change 7.14% 2.35% COMPOSITIONS OF FORMULATIONSTESTED FOR PHOTOSTABILITY BY SCHERING-PLOUGH Ingredients Oil PhaseIngredients  1 Avobenzone 3.00% 3.00%  2 Octisalate 5.00% 5.00%  3Octinoxate (Octyl methoxycinnamate or OMC or MCX) 7.50% 7.50%  4Bemotrizinol (Tinosorb S) 0.00% 2.00%  6 Butyloctyl methoxycrylene***(C12 methoxycrylene or BMOC) 7.00% 5.00%  7 Trideceth-12 1.00% 1.00%  8VP/Eicosene copolymer 1.00% 1.00%  9 Behenyl alcohol + Glycerylstearate + Glyceryl stearate citrate + 1.00% 1.00% Sodiumdicocoylethylenediamine PEG-15 sulfate Total Oil Ingredients 25.50%25.50% Emulsifiers (See 7, 9, 12) 0.00% 0.00% Total Emulsifiers 0.00%0.00% Water Phase Ingredients 10 Disodium EDTA 0.10% 0.10% 11 Xanthangum 0.10% 0.10% 12 Sodium dicocoylethylenediamine PEG-15 sulfate +Sodium 1.00% 1.00% lauroyl lactylate 13 Glycerin 4.00% 4.00% 14 Benzylalcohol 1.00% 1.00% 15 Methylparaben 0.10% 0.10% 16 Propylparaben 0.05%0.05% 17 Water 63.15% 58.15% Total Water Ingredients 69.50% 64.50% OtherIngredients 18 Bisoctrizole (Tinosorb M) 0.00% 5.00% 19Acrylamide/Sodium acryloyldimethyltaurate copolymer (and) 2.00% 2.00%Isohexadecane (and) Polysorbate 80 20 Aluminum starch octenyl succinate3.00% 3.00% Total Other Ingredients 5.00% 10.00% Total 100.00% 100.00%BMOC = Butyloctyl methoxycrylene; TinS = Tinosorb S (Bemotrizinol); TinM= Tinosorb M (Bisoctrizole) UVA1 = total area under curve from 340 to400 nm; UV = total area under curve from 290 to 400 nm PROCEDURE 1.Charge secondary vessel with 1-9. With stirring, heat to 70° C. Continuestirring until homogeneous. Maintain temperature. 2. Charged a thirdvessel with water (19). Dissolve 10 with stirring. Add 11 and stir untilXanthan gum is completely dissolved. 3. Place ⅓ of (2) in primaryvessel. Heat to 65° C. Add 12 and stir until homogeneous. 4. Add oilphase (1-9) to water (10-12) in primary vessel. Homogenize for twominutes, or until emulsion is fully formed. 5. Remove batch from heat.Slowly add balance of water (see Step 2) to emulsion with stirring. Stirwhile cooling. 6. Preblend 13-16. Add to batch with stirring. Add 18 tobatch with stirring. 7. Add 19 and stir until smooth and homogeneous.Add 20 and stir until fully incorporated. Q.S. water. Package when batchis <35° C. Q.S. = quantity sufficient

In addition to the simple ester alkoxy crylene compounds of formula(I)-(V), the alkoxy crylene moieties can be attached as one or moreterminal moieties on a polyester molecule, such as the alkoxyderivatives of the Di (NPG Crylene) Fumerate polyesters disclosed inthis assignee's U.S. Pat. No. 7,235,587 ('587), hereby incorporated byreferences, as shown in formula (VI):

wherein A and B are the same or different and are selected from thegroup consisting of oxygen, amino and sulfur; R¹ and R³ are the same ordifferent and are selected from the group consisting of C₁-C₃₀ alkyl,C₂-C₃₀ alkylene, C₂-C₃₀ alkyne, C₃-C₈ cycloalkyl, C₁-C₃₀ substitutedalkylene, C₂-C₃₀ substituted alkyne, aryl, substituted aryl, heteroaryl,heterocycloalkyl, substituted heteroaryl and substitutedheterocycloalkyl; R² is selected from the group consisting of C₁-C₃₀alkyl, C₂-C₃₀ alkylene, C₂-C₃₀ alkyne, C₃-C₈ cycloalkyl, C₁-C₃₀substituted alkyl, C₃-C₈ substituted cycloalkyl, C₁-C₃₀ substitutedalkylene, C₂-C₃₀ substituted alkyne; R⁴, R⁵, R⁶ and R⁷ are the same ordifferent and are selected from the group consisting of C₁-C₃₀ alkoxystraight chain on branched, and a, b, c and d are each either 0 or 1,and a, b, c and d add up to 1, 2, 3, or 4.

1-78. (canceled)
 79. A method of accepting electronic singlet stateexcited energy from a photon-excited photoactive compound, by absorbingsinglet excited state energy from, and thereby photostabilizing saidphotoactive compound, comprising mixing said photoactive compound with acompound of formula (I):

wherein one of R₁ and R₂ is a straight or branched chain C₁-C₁₂ alkoxyradical, and R₃ is a straight or branched chain C₁-C₂₄ alkyl radical,and exposing the mixture to UV radiation in an amount sufficient for thephotoactive compound to reach an electronic singlet excited state,whereby the compound of formula (I) accepts the singlet excited stateenergy from the excited photoactive compound, thereby returning thephotoactive compound to its ground state so that it is capable ofabsorbing additional UV radiation.
 80. The method of claim 79, whereinR₁ is methoxy and R₂ is hydrogen.
 81. The method of claim 79, wherein R₂is methoxy and R₁ is hydrogen.
 82. The method of claim 81, wherein R₃ isa C₆-C₂₄ straight chain or branched alkyl.
 83. The method of claim 79,wherein the compound of formula (I) is present in an amount in theweight range of 0.1% to 20%, based on the total weight of thecomposition.
 84. The method of claim 83, wherein the compound of formula(I) is present in an amount in the weight range of 0.1% to 10%, based onthe total weight of the composition.
 85. The method of claim 84, whereinthe compound of formula (I) is present in an amount in the weight rangeof 0.1% to 5%, based on the total weight of the composition.
 86. Themethod of claim 79, wherein the molar ratio of the compound of formula(I) to the photoactive compound is less than 0.8.
 87. The method ofclaim 86, wherein the molar ratio of the compound of formula (I) to thephotoactive compound is about 0.1 to about 0.6.
 88. The method of claim84, wherein the compound of formula (I) is present in an amount in theweight range of 3% to 8%, based on the total weight of the composition.89. The method of claim 79, wherein the photoactive compound is selectedfrom the group consisting of p-aminobenzoic acid and salts andderivatives thereof; anthranilate and derivatives thereof;dibenzoylmethane and derivatives thereof; salicylate and derivativesthereof; cinnamic acid and derivatives thereof; dihydroxycinnamic acidand derivatives thereof; camphor and salts and derivatives thereof;trihydroxycinnamic acid and derivatives thereof; dibenzalacetone;dibenzalacetone naphtholsulfonate and salts and derivatives thereof;benzalacetophenone naphtholsulfonate and salts and derivatives thereof;dihydroxy-naphthoic acid and salts thereof; o-hydroxydiphenyldisulfonateand salts and derivatives thereof; p-hydroxydiphenyldisulfonate andsalts and derivatives thereof; coumarin and derivatives thereof; diazolederivatives; quinine derivatives and salts thereof; quinolinederivatives; hydroxyl-substituted benzophenone derivatives;methoxy-substituted benzophenone derivatives; uric acid derivatives;vilouric acid derivatives; tannic acid and derivatives thereof;hydroquinone; benzophenone derivatives; 1,3,5-triazine derivatives;phenyldibenzimidazole tetrasulfonate and salts and derivatives thereof;terephthalyidene dicamphor sulfonic acid and salts and derivativesthereof; methylene bis-benzotriazolyl tetramethylbutylphenol and saltsand derivatives thereof; bis-ethylhexyloxyphenol methoxyphenyl triazineand salts and derivatives thereof; and combinations of the foregoing.90. The method of claim 79, wherein the photoactive compound comprises adibenzoylmethane derivative.
 91. The method of claim 89, wherein thephotoactive compound comprises a dibenzoylmethane derivative selectedfrom the group consisting of 2-methyldibenzoylmethane;4-methyldibenzoylmethane; 4-isopropyldibenzoylmethane;4-tert-butyldibenzoylmethane; 2,4-dimethydibenzoylmethane;2-5-dimethyldibenzoylmethane; 4,4-diispropyldibenzoylmethane;4,4-dimethoxydibenzoylmethane; 4-tert-butyl-4-methoxdibenzoylmethane;2-methyl-5-isopropy-4-methoxydibenzoylmethane;2-methyl-5-tert-butyl-4-methoxydibenzoylmethane;2,4-dimethyl-4-methoxydibenzoymethane;2,6-dimethyl-4-tert-butyl-4-methoxydibenzoylmethane, and combinationsthereof.
 92. The method of claim 79, wherein the photoactive compoundcomprises a combination of a derivative of cinnamic acid and adibenzoylmethane derivative.
 93. The method of claim 92, wherein thederivative of cinnamic acid comprises 2-ethylhexyl-p-methoxycinnamate.94. The method of claim 79, further comprising a diester or polyester ofnaphthalene dicarboxylic acid selected from the group consisting ofcompounds of formula (II) and (III), and combinations thereof:

wherein R₁ and R₂ are the same or different and selected from the groupconsisting of C₁-C₂₂ alkyl groups, diols having the structure HO—R₄—OH,and polyglycols having the structure HO—R₃—(—O—R₄—)_(n)—OH; wherein eachR₃ and R₄ is the same or different and selected from the groupconsisting of C₁-C₆ straight or branched chain alkyl groups; and whereinm and n are each in a range of 1 to
 100. 95. The method of claim 94,comprising a diester of formula (III) wherein R1 and R2 are2-ethylhexane.
 96. The method of claim 79, wherein said mixture includesa cosmetically acceptable carrier.
 97. The method of claim 79, whereinsaid mixture includes an oil phase having a dielectric constant of atleast about
 8. 98-101. (canceled)